Pyrolytic conversion of hydrocarbons with the aid of a fluidized catalyst



July l2, 1949. w. s. GULLETTE PYROLYTIC CONVE RSION OF HYDROCARBONS WITH THE AID OF A FLUIDIZED CATALYST Filed April 30, 1947 Pamuk, dvmrmolmmnn 14mm ATTORNEYS `thereacxtion zone.,k important consideration in operations off' aspect,l isV the utilizai Patented July 12, 1949 nousl wrm 'ma CArALYsT 2,476,144 A,Pylimlazir'lo CONVERSION 10F wma s'. ouueaamihima, ma., asminnfai` sa.

clair Refining Company, New York,kN. Y., a v corporation of Maine Application April 30, 1947,' Serial o. 715,047

This invention relates sion of hydrocarbons and, more particularly, to

pyrolytic conversion processes involving the usev ofiin'ely divided catalyst. f v

The invention is especially applicable to conversion processes of the general .type `wherein ay suspension of nely divided catalyst in oil vapors, at an elevated temperature, isapassed to a reactor in which conversion of the oil occurs and infwhich thespent catalyst-is separated from--the-foll vapors, the separated catalyst strippedfof oil, regenerated and the regenerated catalyst again suspended in the stream of oil vaporspassing to the reactor. Operations ofthe type described are commonly designated fluid catalyst-processes. In conventional operation, the spent `catalyst from the stripping` zonefis conveyed, lin suspension in a gaseous medium-to a regenerating zone-in which to the pyrolytic conver-A acmms. (ol. 19d-52) thecarb'on'deposited onthe catalyst. particles erated-catalyst iniluid suspensinjis `ret iirned tof y this type, froml a practical tion of the catalyst to the lfullest extentpossible.

For mxfmmnfemciency, it; is 'desirbieftnatall c ofthecata'lyst be utilized to an equal extent in the-.reaction zoneand passed to the regenerator and that, inf-thelr'egenerator, allQthe-catalyst beA uniformly regeneratedrand returned tothe vrem:-

tionzone.

In4 operations ly maintained throughout thev operation in Ja iiuidized, i. e.,' a free-'owi'ng condition, However, the catalyst is normallynot of uniform density throughout' thefwarious lstages -o t g the operation.

In the reactor, for instance', thereis a rela" tively dense phase `AbodyV ofthefcatalyst which is kept iiuidized Vby the hydrocarbon vapors 'pass ing therethroughv and from which the spent catalyst is withdrawn forregeneration. A similar. dense phase body of the/'catalyst is r'naintainedv in the.A regenerator, from" which regenerated :catalyst is withdrawn' and returnedfto thereactor. In both the reaction zone 'andthe regenerating zone, there is Anormally this so-called high density. or dense phase body o f 'catalyst above which'the catalyst, in'relativel'y.` vlow concentraf The particles of the'catalystvary considerably in size and there'is a tendency'lfor the larger particles to gravitate to the lower portion 'of the dense phase body of catalyst in the reaction of this type,.the .catalyst usual- L zone and in the regenerating zone and for the smaller particles to be carried to the'upper por'I tion-of the dense phase bodyof thecatalyst.` l By 4reason of this 'tendency toward stratlcationythe larger particles of the catalyst are nor--l mally more rapidly circulated through the system' than are .the smaller particles.- l large proportion ofv thesmaller particlesV of the catalyst` is carried off from there'generator with theweilluent gases to the precipitator from which it is normally returned to the regenerating zone,

and frequently is repeatedly recycledbetween the regenerator and precipitator and subjected to afgreater period of time than desirablein the regenerating'zonek insteadfof being returned to the reactor.r Atth'e'same time, larger particles of the catalyst maybe too rapidly removed from theregenerating zone before they have been completely regenerated.` A` .similarl condition exists l in the Ireactor`- In,mycopendingapplicatin Ser.I No, '7451346l filed concurrently, herewith, I have `disclosed andv claimed an improved method of operation wherebyfthelack of uniformity` f` circulation ofv the catalyst through thelsyste'm'ia to a-major extent, avoided. 'In.acco'rdan ce withthe process there described, ythe catalyst" isuniformly withdrawn for recirculation from .thereac'tion zoneA to'the regenerating zoneand from A,the regeneratingzone backto the reaction zone, respectively, from over substantially the r,entire depth of the above described high.ldensity of dense phase -body of the catalyst. I.. 1

The present invention constitutes an improve` ment in @the methodgof operation described in my above noted application and provides a methodiof, operationv Wherebycfurther' improvement in the uniformity of' catalyst kcirculation vthrough the system' is attained, particula'rly withgrespect to the `fines o 'r'nely "divided particles of catalyst carried offV from the' in the eiiluent flue gases.

These nes are, tosome extent,`present'in the i cip ator- 'and' the regenerator without passing to the lines directly from the precipitator, in which Frequently, a-

ageneratort in suspension its central portion over a anni height of the dense phase body. 'By the Joint use of my direct return of the lines to the reaction sone and the uniform withdrawal ofy spentL catalyst from the reaction sone, 4the rines are y effectively recycled and continuously utilized in the system.

The mvenuen wm be more muy described and illustrated by reference to the accompanyingV drawing which represents conventionally and diagrammatically a flow .diagram ofa iiuidcatalyst cracking operation embodying my invention.

The apparatus illustrated by the reference numeral I (of Fig. l) of the drawing represents a generally cylindrical reactor. The finely divided catalyst 'suspended in oil vapors enters the reactor through the conduit 2 extending into the reactor and terminating in a conical member 3 of somewhat smaller'v maximum that of the reactor. Just above the conical meinber l. there 4is positioned a plate 4, perforated at diameter equal to the maximum diameter of the conical member 3 and otherwise imperforate except for four openings through the plate spaced 9c apart from which there extend upwardly four risers or standpipes l.

Asthehotoilvaporspassimwardlythrough the reactor there is a tendency for the catalyst to drop out of suspension and gravitate downs wardly through the reaction sone forming the highdensity" or dense phase body of catalyst, as previously described.

The oil vapors, product of the conversion, rise to the top'ofthe reactor, pass through a cyclone separator C, to remove suspended catalyst from the vapors. the latter passing therefrom through previously described meth'.v drawing spentcatalyst from the reactor from over substantiallythe entirefld bed is permitted freer access to thestandpipe than is the more dense catalyst at the lower portion of the bed. l

The' spent catalyst passing downwardly through the standpipes d iiows intothe conical lower portion ofthe reactor and passes downwardly through spent catalyst leg I, in winch there is interposed a valve arrangement il, advantageously of the double slide valve type, and into conduit Il where it is caught up by a current of stripping medium introduced through line l2 and carried up into the bottom of stripper Il.

The stripping medium introduced through line l2 may be steam. for instance, but in the operation shown, the stripping medium is hot ilue gases from the regenerator presently to be described.- The spent catalyst leg l is, advantageously, of suilicient-length to form an eective seal against the upward passage of stripping medium into the reactor.

ou le pintnmyr strippeslfrem the catalyst in transit to the stripper and further stripping is thereafter eifected in the stripper. The stripper il is provided with a plurality of bailes or pertorated plates is adaptedto retard the passage of catalyst upwardly through the stripper and to promote uniform and prolonged contact between the catalyst and the stripping medium supplied through line I2.

Gaseous products pass from the top of the vstripper through a cyclone type separator il, for

' scrubbed with a scrubbing menstruum, for inconduit I to fractionating apparatus. not shown,

and the separated catalyst droppingback into the reactor to a sone thereof below the upper surface of the high density body of catalyst.

Each of the staudlilles I is provided with slots or other openings l in opposite sides thereof.

^ preferably placed at 90' to the radius of the reactor running through the center of the standpipe.

These standpipes I are preferably of such height as to `extend well above the top level of the socalled dense phase. The slots should be spaced along the entire height of the standpipes, or atleast to a height equal to that of the dense phase body of the catalyst. The area of the slots should be such that the summation of their area doesl 'not greatly exceed that of the transverse sectional area of the vertical passage through `the respective standplpes. I Y

InsteadV of a plurality of openings I placed along rthe height of the respective standpipes, each standpipe may be provided with a' slot on opposite sides thereof. extending the entire height of the standpipe.

In order further to regulate thevilow ofthe catalyst into the respective standpipes, the slot may be of V-shape, being larger at its upper end. Further, the areas of the respectivel openings I mayI be progressivelylarger from bottom toitOil for the same reason. By this arrangement@ the less dense catalyst from the upper portion ofthe stance. water' or oil, to separate valuable hydrol carbons from the incondensible gases. The scrubbed gases pass out through conduit is and the scrubbing menstruum and absorbed hydrocarbons pass through line il to a separator, diagrammatically represented at il. fromwhich they y menstruum passes through line 2i and the hydrocarbons pass oir through line 22 and may be returned for retreatment or passed to storage.

The hot stripping .medium passing upward through the stripper, strips from the catalystthe maior portion ofv vaporisable hydrocarbons contained therein and carries the catalyst gradually lupwardly through the stripper. A relatively dense bed ofthe catalyst accumulates in the stripper and overflows through conduit 23 to thev upper portion of the regenerator 2l. A small amount of stripping medium. steam or nue gases. for instance, may be introduced into the lower end of conduit 23 through line 2l for the purpose of maintaining the catalyst in a fluid condition4 and also further to strip from the catalyst any .residual oil or vapors.

The regenerator shown is of a cylindrical type,

quite similar to the reactor, just described, ex

cept that the catalyst inlet conduit leads to the upper portion of the regenerator,

Positioned in the lower portion of the regenc erator. just above the cone shaped bottom of the regenerator, ls a plate 2t. perforated at its center portion and otherwise imperforate except for four openings therethrough spaced 90 apart. each opening connecting the lower conicalportion of the regenerator with an upwardly proiectlng standpipe 21 similar to thestandpipes l f' of the reactor. As in the reactor, these standpipes extend upwardly to a point preferably well above the top level of the so-called dense phase of the body of catalyst in the regenerator and' .may extend the entire helghtlof standpipe, the

size of the opening being either parallel or forming a V-shaped slot. It is desirable, however, that the summation of the areas oi' the openings in any one standpipe not greatly exceed the crosssectional air of the vertical passage extending through the standpipe.

Upon contact of the air with the hot catalyst, the coke or carbon deposited on the catalyst is burned as the catalyst gravitates gradually downwardly through the regenerator, air being introduced in the lower portion oi' the regenerator through line 28.

The air and products of combustion passing upwardly through the regenerator tend to carry the smaller particles of catalyst along in suspension and maintains the bed in a fluid condition.

The products of combustion pass from the upper portion of the regenerator through cyclone separator 30 for the separation of a portion oi' the catalyst remaining in suspension in the flue gases. The separated catalyst is returned to a point in the regenerator below the upper surface of ythe dense phase of the body of catalyst and the products of combustion carrying catalyst iines in suspension pass through conduit 3| to a precipitator of conventional type. for instance, an electrical precipitator, diagrammatically represented on the drawing at 32.

The regenerated catalyst is withdrawn through standpipes 21 from zones spaced or extending along the entire height of the catalyst bed, and passed by gravity into the lower conical portion of the regenerator and out through regenerated catalyst leg 33 into the lower end of conduit 2 where it is caught up by a stream of preheated charge oil and returned to the reactor, as previously described. 'I'he regenerated catalyst -leg is provided with a valve arrangement 34, advantageously oi' the double slide valve type, for controlling the passage of catalyst from the regenerator, and the leg is advantageously of suillcient length to form an eifective seal against the upward passage of charge oil to the regenerator.

The precipitated fines are passed from the precipitator 32 through conduit 35 linto hopper 36 and from the hopper through conduit 31, controlled by valve 38, into the lower` end of the reactor feed line 2 and carried along by the charge oil, together with the catalyst from the regenerated catalyst leg, directly to the reactor.

A portion of the flue gases passing from the precipitator through line 35 is diverted through line 40 by means of booster 4l and passed through line I2 into the lower end of conduit Il, as previously described.

'I'he catalyst employed may be of the type conventionally used in fluid catalyst processes, for instance, a silica-alumina type catalyst in iinely divided or powdered form. The reaction conditions may, likewise, be those conventionally used in operations of this type and. as understood by the art, the optimum temperatures and pressures will depend primarily upon the type of feed stock used, the particular catalyst employed, and the reaction desired.

In cracking gas oil, for instance, the reaction temperature may, with advantage, be within the range of about 800 to 1,000 F. and the pressure at the top of the reactor within the range of about 5. to 25 pounds per square inch. The regeneration temperature may be within the range of about 950 to 1,200 F. The nue gases passing from the regenerator will usually be under a pressure oi' about 5 to 15 pounds per square inch and this pressure is,l with advantage, boosted to, say, 25 pounds per square inch or higher by the booster.

It will be understood that the present invention is not restricted to the particular embodimentherein described, but is applicable to various modifications ot fluid catalyst processes.

Further, it will be understood that the term gaseous medium is used in the appended claims to designate the medium to be brought into contact with the catalyst and, in addition to true gases, is intended -to include vapors.

I claim:

1. In the iluid catalyst process for the conversion of hydrocarbons, in which the hydrocarbon in vapor phase is passed upwardly through a relatively dense iluidized body of the catalyst in a reaction zone, spent catalyst is withdrawn from the reaction zone, stripped of oil, regenerated by passing a stream of gaseous regenerating medium in contact therewith, regenerated catalyst is returned to the reaction zone, and residual catalyst nes passed from the regenerating zone in suspension in eilluent gases, the improvement which comprises uniformly withdrawing the catalyst for regeneration from throughout the height of the relatively dense body of the catalyst in the reaction zone, separating the residual catalyst nes from the eiliuent gases from the regenerating zone and positively returning the separated nes directly to the reaction zone.

2. In the fluid catalyst process for the conversion of hydrocarbons in which the hydrocarbon in vapor phase is passed upwardly through a relatively dense iluidized body of the catalyst in a reaction zone, spent catalyst` is withdrawn from the reaction zone, stripped of oil, passed to a regenerating zone and regenerated therein by passing a gaseous regenerating medium upwardly through a relatively dense fluidized body of the catalyst from which regenerated catalyst is withdrawn and returned to the reaction zone and residual catalyst lines pass oil from the regenerating zone in suspension in etiluent gases, the improvement which comprises uniformly withdrawing catalyst for recirculation from throughout the height of the'respective relatively dense uidized bodies of the catalyst, separating residual catalyst lines from the eiiluent gases from the regenerating zone and positively returning the separated lines directly to the reaction zone.

3. In the iluid catalyst process for the conversion of hydrocarbons wherein a nely divided solid catalyst suspended in charge oil is passed to a reaction'zone, wherein a dense phase uidized body of the catalyst is formed and the charge oil is passed in vapor phasel upwardly through the body of catalyst, spent catalyst is withdrawn from the reaction zone, stripped of oil and regenerated in a regenerating zone by passing a stream of regenerating gases in contact therewith, regenerated catalyst is returned to the reaction zone and residual catalyst fines passed from the regenerating zone in suspension in eilluent gases, the steps oi' continuously withdrawing catalyst for regeneration from the dense phase body of catalyst in the reaction sone from a plurality of points uniformly spaced along its height, sepmtinl' the residual catalyst time from the eiiluent nu: from Theiollowlnir referenlces :r of record ln the nale oi this pgtent: y

v BTA'IEB PAIENTB the resenerator and positively returning the Igp; Nixmber l Name y l Date :rated ilnes directly to the reaction none. 2.334.553 Hujdinz Nov. r16. 1943 WILLIEl s. 'cmnnl'rx'm 5 :3.33 Edmmer',1. June 19, 194s REFERENCES crrnn l 224031943 mcnnuon`f neo. 1a', ma nemer ..'...out` a. me 

